DE1794385C3 - Anthraquinone dyes - Google Patents
Anthraquinone dyesInfo
- Publication number
- DE1794385C3 DE1794385C3 DE1794385*CA DE1794385A DE1794385C3 DE 1794385 C3 DE1794385 C3 DE 1794385C3 DE 1794385 A DE1794385 A DE 1794385A DE 1794385 C3 DE1794385 C3 DE 1794385C3
- Authority
- DE
- Germany
- Prior art keywords
- radical
- group
- anthraquinone
- formula
- bis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/35—Ketones, e.g. benzophenone
- A61K8/355—Quinones
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
- A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/002—Dyes with anthracene nucleus not condensed with any other ring containing onium groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/16—Amino-anthraquinones
- C09B1/20—Preparation from starting materials already containing the anthracene nucleus
- C09B1/207—Dyes with amino groups and with onium groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/16—Amino-anthraquinones
- C09B1/20—Preparation from starting materials already containing the anthracene nucleus
- C09B1/26—Dyes with amino groups substituted by hydrocarbon radicals
- C09B1/262—Dyes with no other substituents than the substituted amino groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/16—Amino-anthraquinones
- C09B1/20—Preparation from starting materials already containing the anthracene nucleus
- C09B1/26—Dyes with amino groups substituted by hydrocarbon radicals
- C09B1/28—Dyes with amino groups substituted by hydrocarbon radicals substituted by alkyl, aralkyl or cyclo alkyl groups
- C09B1/285—Dyes with no other substituents than the amino groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/16—Amino-anthraquinones
- C09B1/20—Preparation from starting materials already containing the anthracene nucleus
- C09B1/26—Dyes with amino groups substituted by hydrocarbon radicals
- C09B1/32—Dyes with amino groups substituted by hydrocarbon radicals substituted by aryl groups
- C09B1/325—Dyes with no other substituents than the amino groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
- C09B1/501—Amino-hydroxy-anthraquinones; Ethers and esters thereof containing onium groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
- C09B1/51—N-substituted amino-hydroxy anthraquinone
- C09B1/515—N-alkyl, N-aralkyl or N-cycloalkyl derivatives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
- C09B1/51—N-substituted amino-hydroxy anthraquinone
- C09B1/515—N-alkyl, N-aralkyl or N-cycloalkyl derivatives
- C09B1/5155—N-alkyl, N-aralkyl or N-cycloalkyl derivatives only amino and hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/78—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with other reactive groups
- C09B62/80—Anthracene dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/30—Material containing basic nitrogen containing amide groups furs feathers, dead hair, furskins, pelts
- D06P3/3033—Material containing basic nitrogen containing amide groups furs feathers, dead hair, furskins, pelts using basic dyes
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Emergency Medicine (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Cosmetics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Coloring (AREA)
- Hydrogenated Pyridines (AREA)
Description
bdie tertiären oder quarteruären Derivate verwendetbthe tertiary or quarteruary derivatives are used
^Außerdem ist die Löslichkeit dieser Farbstoffe in Wasser infolge der Anhäufung von basischen Gruppen «esentHch verbessert, wodurch es möglich ist, wäßrige Färbelösungen mit einer Konzentration von über 10% rü erhalten.^ In addition, the solubility of these dyes in water is improved due to the accumulation of basic groups "esentHch, whereby it is possible to obtain aqueous staining solutions rü with a concentration of over 10%.
Ein weiterer schätzenswerter Vorteil Tür die Haarkunst liegt in der Widerstandsfähigkeit der mit Hilfe dieser Farbstoffe erhältlichen Färbungen gegen das Sonnenlicht. So entspricht ihre Haltbarkeit annähernd dem Wert 4 der von der Gesellschaft zur Bestimmung der Echtheit von Textilfaden und -drucken (vgl. rode de soliditc, editc par le Groupement d Etudee Continental Europeen, 2. Ausgabe [1958], S. 31) aufgestellten Skala, wenn dieser Wert und die erhaltenen Falben gleichzeitig und unter denselben Bedingungen dem Sonnenlicht ausgesetzt werden.Another valued benefit door the hair art lies in the resistance of the dyeings obtainable with the help of these dyes to the Sunlight. So their shelf life corresponds approximately to the value 4 that of the society for determination the authenticity of textile threads and prints (cf. rode de soliditc, editc par le Groupement d Etudee Continental Europeen, 2nd edition [1958], p. 31) established scale if this value and the received pinks at the same time and under the same conditions exposed to sunlight.
Diese Skala umfaßt Werte von 1 bis 8, wobei die Stufe 8 der besten Echtheit entspricht. Andererseits kann man durch eine entsprechende Wahl der Stellung der beiden Aminogruppierungen des Anthrachinonmoleküls Farbstoffe erhalten, die sehr verschiedene Nuancen ergeben, und zwar von Rot bis Blau und Blaugrün. Durch entsprechendes Mischen der Farben können sehr leicht die gewünschten natürlichen Farbtönungen erhalten werden.This scale includes values from 1 to 8, with level 8 corresponding to the best authenticity. on the other hand can be achieved by an appropriate choice of the position of the two amino groups of the anthraquinone molecule Get dyes that give very different shades, from red to blue and Blue green. By mixing the colors appropriately, you can very easily create the desired natural Shades of color are obtained.
Ein weiterer Vorteil der erfindungsgemäßen Verbindungen bei der Anwendung zur Haarfärbung besteht darin, daß diese Verbindungen bei ihrer Anwendung keinen unangenehmen Geruch entwickeln.Another advantage of the compounds according to the invention when used for coloring hair is that these compounds do not develop an unpleasant odor when used.
Es ist möglich, eine oder mehrere erfindungsgemäße Verbindungen in Haarfärbemitteln anzuwenden, wobei Färbungen von Rot bis Blaugrün erhalten werden. Es ist weiterhin möglich, die erfindungsgemäßen Verbindungen mit anderen üblicherweise zum Haar-It is possible to use one or more compounds according to the invention in hair dyes, wherein Colorations from red to blue-green can be obtained. It is also possible to use the invention Connections with others usually related to hair
färben verwendeten Farbstoffen zu mischen, um andere Nuancen zu erhalten.dye to mix the dyes used to get other nuances.
Die erfindungsgemäßen Verbindungen werden als Haarfärbemittel im allgemeinen in Form einer wäßrigen Lösung verwendet, die sehr leicht durch Lösen einer oder mehrerer erfindungsgemäßer Verbindungen in Wasser, gegebenenfalls im Gemisch mit anderen bekannten Farbstoffen, hergestellt werden kann. Diese Färbelösungen können außerdem verschiedene in der Kosmetik üblicherweise verwendete Produkte, wie Dispergiermittel, Weichmacher oder Riechstoffe zugesetzt werden. Der pH-Wert dieser Färbelösungen kann in weiten Grenzen schwanken, er wird jedoch im allgemeinen zwischen 3 und 10, vorzugsweise zwischen 4,5 und 9,5 gehalten.The compounds according to the invention are generally used as hair colorants in the form of an aqueous one Solution used very easily by dissolving one or more compounds according to the invention can be prepared in water, optionally mixed with other known dyes. These Coloring solutions can also contain various products commonly used in cosmetics, such as Dispersants, plasticizers or fragrances are added. The pH of these staining solutions can vary within wide limits, but it is generally between 3 and 10, preferably between 4.5 and 9.5 held.
Die unter Verwendung der erfindungsgemäßen Verbindungen erhältlichen Haarfärbemittel werden in üblicher Weise auf die Haare aufgebracht, vorzugsweise bei gewöhnlicher Temperatur. Die Konzentrationen an erfindungsgemäßem Farbstoff können entsprechend dem gewünschten Zweck in weiten Grenzen variieren.The hair dyes obtainable using the compounds according to the invention are described in Usually applied to the hair, preferably at ordinary temperature. The concentrations according to the desired purpose, the dye according to the invention can be used within wide limits vary.
Die erfindungsgemäßen Verbindungen werden erhalten, indem man auf Chinizarin oder 1,5- bzw. 1,8-Dichloranthrachinon ein Diamin der Formel H2N -YZ einwirken läßt, wobei Y und Z die oben angegebenen Bedeutungen besitzen.The compounds according to the invention are obtained by allowing a diamine of the formula H 2 N -YZ to act on quinizarin or 1,5- or 1,8-dichloroanthraquinone, where Y and Z have the meanings given above.
Die Quarternisierung der so erhaltenen tertiären Anthrachinonderivate kann sehr leicht in üblicher Weise durch Einwirkung eines Quarternisierungsmittels, wie Dimethylsulfat oder eines Aikylhalogenids, gegebenenfalls in Gegenwart eines geeigneten Lösungsmittels erfolgen.The quaternization of the tertiary anthraquinone derivatives obtained in this way can very easily be carried out in the usual way Way through the action of a quarternizing agent, such as dimethyl sulfate or an alkyl halide, optionally in the presence of a suitable solvent take place.
Die nachfolgenden Beispiele erläutern die Erfindung im Hinblick auf die Herstellung und die Verwendung der erfindungsgemäßen Verbindungen.The following examples explain the invention with regard to production and use of the compounds according to the invention.
Beispiele für die Herstellung von erfindungsgemäßen VerbindungenExamples of the preparation of compounds according to the invention
Beispiel 1 Herstellung von l,4-Bis-(/i-morpholinoäthylamino)-anthrachinonexample 1 Production of 1,4-bis (/ i-morpholinoäthylamino) -anthraquinone
CH2-CH2 CH 2 -CH 2
O NH-CH2-CH2-NO NH-CH 2 -CH 2 -N
CH2-CH2
CH2-CH2
O NH-CH2-CH2-N OCH 2 -CH 2
CH 2 -CH 2
O NH-CH 2 -CH 2 -NO
Ein Gemisch von 0,06 Grammol Chinizarin, 0,06 Grammatome Zink und 0,2 Grammol /i-Aminoäthylmorpholin in 100 cm3 Isobutanol wird 3 Stunden am Rückfluß gekocht.A mixture of 0.06 gramol quinizarine, 0.06 gram atom zinc and 0.2 gramol / i-aminoethylmorpholine in 100 cm 3 isobutanol is refluxed for 3 hours.
Nachdem das als Zwischenprodukt gebildete Leukoderivat oxydiert und das Zink abfiltriert wurde, wird das erhaltene Gemisch zur Trockne eingedampft und der Rückstand in Benzol gelöst. Die Lösung wird hierauf mit einer 10%igen Sodalösung gewaschen, dann getrocknet und zur Trockne eingedampft.After the leuco derivative formed as an intermediate product has been oxidized and the zinc has been filtered off, is the resulting mixture was evaporated to dryness and the residue was dissolved in benzene. The solution will be then washed with a 10% soda solution, then dried and evaporated to dryness.
Man erhält das gewünschte Produkt in einer Aus-6o beute von 90%. Dieses Produkt, aus Hexan umkristallisiert, schmilzt bei 157° C.The desired product is obtained in a yield of 90%. This product, recrystallized from hexane, melts at 157 ° C.
Analyse:Analysis:
Berechnet
gefunden .Calculated
found .
C 67,24,
C 67,15,
C 66,93,C 67.24,
C 67.15,
C 66.93,
H 6.89. H 7.00. H 6.91.H 6.89. H 7.00. H 6.91.
\ 1106%; N 11.87%; N 11,77%.\ 1106%; N 11.87%; N 11.77%.
Beispiel 2
Herstellung von [Anthrachinon-!,4-bis-!aminoäthyl-/MN-methylmorpholinium):]-bis-methosulfalExample 2
Production of [anthraquinone - !, 4-bis-! Aminoethyl- / MN-methylmorpholinium):] - bis-methosulfal
CH2-CH,CH 2 -CH,
NH - CH2 CH2 NNH - CH 2 CH 2 N
CH3-CH,CH 3 -CH,
CH2-CH,CH 2 -CH,
NH — CH, - CH, — NNH - CH, - CH, - N
CH2CH2 CH 2 CH 2
2(SQ1CH, )2 (SQ 1 CH,)
Dieses Produkt wird in einfacher Weise durch Einwirkung von Dimethylsulfat auf die entsprechende Base unter Rückflußkühlung und unter Verwendung von Toluol als Lösungsmittel erhalten. Das aus Methanol umkristallisierte Produkt schmilzt unter Zersetzung bei 240 bis 245 C.This product is obtained in a simple manner by the action of dimethyl sulfate on the corresponding base under reflux cooling and using toluene as solvent. The product recrystallized from methanol melts with decomposition at 240 to 245 C.
Analyse:Analysis:
Berechnet ... N 7,82%;
gefunden .... N 7,77, 7,60%.Calculated ... N 7.82%;
found .... N 7.77, 7.60%.
Beispiel 3
Herstellung von 1,5-8is-(/i-morpholinoüthylamino)-anthrachinonExample 3
Preparation of 1,5-8is - (/ i-morpholinoüthylamino) -anthraquinone
CH2-CH2 CH 2 -CH 2
O NH CH, -CH, NO NH CH, -CH, N
CH2-CH2 CH 2 -CH 2
CH2-CH2 CH 2 -CH 2
O NCH2-CH2 HN OO NCH 2 -CH 2 HN O
CH2-CH2 CH 2 -CH 2
Dieses Produkt wird durch Umsetzung von /f-Aminoäthylmorpholin in geringem Überschuß mit 1.5-Dichloranthrachinon unter Sieden am Rückfluß während 6 Stunden erhalten, wobei Isobutanol als Lösungsmittel zur Verwendung gelangt. Nach dem Abkühlen lallt das Rohprodukt aus. welches durch mehrmaliges Umkristallisieren aus Alkohol gereinigt wird. Schmelzpunkt: 203 C.This product is obtained by reacting / f-aminoethylmorpholine in a slight excess with 1,5-dichloroanthraquinone obtained under reflux for 6 hours, using isobutanol as the solvent Use. After cooling, the crude product lalls out. which by repeated recrystallization is purified from alcohol. Melting point: 203 C.
Analyse:Analysis:
Berechnet ... C 67,24, H 6,89, N 12,06%; gefunden .... C 67,12, H 6,75, N 11,85%;Calculated ... C 67.24, H 6.89, N 12.06%; found .... C 67.12, H 6.75, N 11.85%;
C 67.23, H 6,78. N U,80%.C 67.23, H 6.78. N U, 80%.
Beispiel 4
Herstellung von fAnthrachinon-l,5-bis-{aminoäthyl-/i-(N-niethylmorpholinium)(]-bis-melhosulfatExample 4
Production of fAnthraquinone-1,5-bis- {aminoethyl- / i- (N-niethylmorpholinium) (] - bis-melhosulfate
CH2-CH2 CH 2 -CH 2
O NH-CH2-CH2-N OO NH-CH 2 -CH 2 -NO
CH2-CH2 CH 2 -CH 2
CH,CH,
/ \ II!/ \ II!
O N — CH2 — CH2 — HN OON - CH 2 - CH 2 - HN O
CH2 CH2 CH,CH 2 CH 2 CH,
CH2-CH2 CH 2 -CH 2
2(SO4CH1-)2 (SO 4 CH 1 -)
Dieses Produkt wird in üblicher Weise aus der Base gemäß Beispiel 3 durch Einwirkung von Dimethylsulfal ι Toluol erhalten: es schmilzt unter Zersetzung hei 250 C.This product is made in the usual way from the base according to Example 3 by the action of dimethyl sulfal ι Get toluene: it melts with decomposition at 250 C.
analyse:analysis:
Berechnet ... N 7,54%:
gefunden .... N 7.56. 7.65%.Calculated ... N 7.54%:
found .... N 7.56. 7.65%.
Beispiel 5
Herstellung von 1.4-Bis-(iM-morpholinohexylamino)-anthrachinonExample 5
Production of 1,4-bis- (iM-morpholinohexylamino) -anthraquinone
CH2-CH2 CH 2 -CH 2
O NH -(CH2),,- NO NH - (CH 2 ) ,, - N
Jl 1Jl 1
CH2-CH7 CH 2 -CH 7
CH2-CH, CH,-CH,CH 2 -CH, CH, -CH,
Wie im Beispiel 1 wird ein Gemisch von Chinizarin, Zinkpulver und <>-Aminohexylmorpholin in lsobutanol während 4 Stunden unter Rühren am Rückfluß erhitzt. Nach Verdampfen usw. erhält man das gewünschte %odukt in einer Ausbeute von 50%. Nach Umkristallisieren aus Heptan schmilzt das Produkt bei 71 C.As in Example 1, a mixture of quinizarin, zinc powder and <> - Aminohexylmorpholine in isobutanol heated under reflux for 4 hours with stirring. After evaporation, etc., the desired one is obtained % oduct in a yield of 50%. After recrystallization from heptane, the product melts at 71 C.
Analyse:Analysis:
Berechnet ... C 70.83. H 8.33, N 9.72%:Calculated ... C 70.83. H 8.33, N 9.72%:
gefunden .... C 70,87, H 7.97, N 9.57%;found .... C 70.87, H 7.97, N 9.57%;
C 70,98. H 8,27, N 9.50%.C 70.98. H 8.27, N 9.50%.
Beispiel 6
Herstellung von [Anthrachinon-l^-bis-laminohexyl-oi-fN-methylmorpholiniumJiJ-bis-methosulfatExample 6
Preparation of [Anthraquinone-l ^ -bis-laminohexyl-oi-fN-methylmorpholiniumJiJ-bis-methosulfate
CH2-CH,
NH-(CH2I6-N OCH 2 -CH,
NH- (CH 2 I 6 -NO
2(SO4CH3-)2 (SO 4 CH 3 -)
\ CH2 CH2 \ CH 2 CH 2
CH3 CH 3
CH2-CH2 NH - ICH,)* - N OCH 2 -CH 2 NH - ICH,) * - NO
CH2-CH2 CH 2 -CH 2
Dieses Produkt wird durch Quarternisienmg der im Beispie! 5 beschriebenen tertiären Base mittels Dimethylsulfat hi Toluol durch Sieden am Rädkflu8 erhalten Das Produkt ist sehr hygroskopisch und wed daher sofort ohne Reinigtrag verwendet.This product is made by quartering the in the example! The tertiary base described in 5 can be obtained by means of dimethyl sulfate hi toluene by boiling on the Rädkflu8. The product is very hygroscopic and therefore wed immediately used without cleaning agent.
Beispiel 7 Herstellung von 1.8-B»-(^-fmirphoHnoä«hv}amnio)-anthrachmonExample 7 Production of 1.8-B »- (^ - fmirphoHnoä« hv} amnio) -anthrachmone
CH2-CH2 CH 2 -CH 2
CH2CH2 CH 2 CH 2
CH2-CH2 CH 2 -CH 2
Ii οIi ο
ftft
^^
Dieses Produkt wird auf die gleiche Weise wie das Produkt gemäß Beispiel 3 erhallen, indem man auf 1.8-Dichloranthrachinon /f-Aminoüthylinorpholin einwirken läßt; aus Hexan umkristallisiert, schmilzt es bei 170 bis 17PC.This product is obtained in the same way as the product according to Example 3, adding to 1.8-dichloroanthraquinone / f-Aminouthylinorpholine can act; recrystallized from hexane, it melts at 170 up to 17PC.
Analyse:Analysis:
Berechnet ... C 67.24. H 6.89. N 12,06%:Calculated ... C 67.24. H 6.89. N 12.06%:
gefunden .... C 67,27, H 7.16. N 12.37%:found .... C 67.27, H 7.16. N 12.37%:
C 67,03. H 6.96. N 12.25%.C 67.03. H 6.96. N 12.25%.
Beispiel 8
Herstellung von [Anthrachinon-l.S-bis-iaminoäthyl-p'-lN-methylmorpholiniumKj-bis-methosulfatExample 8
Production of [Anthraquinone-IS-bis-iaminoethyl-p'-IN-methylmorpholiniumKj-bis-methosulfate
CH2-CH2 CH2-CH2 CH 2 -CH 2 CH 2 -CH 2
O N-CH2-CH2-HN O NH-CH2-CH2-N OO N-CH 2 -CH 2 -HN O NH-CH 2 -CH 2 -NO
CH2-CH2 CH 2 -CH 2
CH3 CH 3
CH5-CH,CH 5 -CH,
Ausgehend von der entsprechenden Base wird dieses Produkt durch Umsetzung mit Dimethylsulfat in üblicher Weise hergestellt. Aus Alkohol umkristallisiert, schmilzt das Produkt unter Zersetzung bei 200 bis 201 C.Starting from the corresponding base, this product becomes customary by reaction with dimethyl sulfate Way made. Recrystallized from alcohol, the product melts with decomposition at 200 to 201 C.
Beispiel 9
Herstellung von 1,4-Bis-( ;-piperidinopropyl-amino)-anthrachinonExample 9
Preparation of 1,4-bis- (; -piperidinopropyl-amino) -anthraquinone
O NH-CH,-CH,-CH,-NO NH-CH, -CH, -CH, -N
CH,CH,
CH2-CH2 CH 2 -CH 2
O NH — CH2 - CH2 — CH2 — N \?H,O NH - CH 2 - CH 2 - CH 2 - N \? H,
CH2-CH2 CH 2 -CH 2
Wie im Beispiel 1 wird ein Gemisch von Chinizarin, Zinkpulver und y-Aminopropyl-piperidin in Isobutanol während 10 Stunden am Rückfluß gekocht. Nach Verdampfen usw. erhält man das gewünschte Produkt in einei Ausbeute von ungefähr 50%. Aus Petroläther und Alkohol umkristallisiert, schmilzt es bei 123° C.As in Example 1, a mixture of quinizarine, zinc powder and γ-aminopropyl-piperidine in isobutanol refluxed for 10 hours. After evaporation, etc., the desired product is obtained in one form Approximately 50% yield. Recrystallized from petroleum ether and alcohol, it melts at 123 ° C.
Analyse:Analysis:
Berechnet... C 73,77, H 8,19%:Calculated ... C 73.77, H 8.19%:
gefunden .... C 73,83, H 8,18%:found .... C 73.83, H 8.18%:
C 73,8Z H 8,23%.C 73.8Z H 8.23%.
Beispiel 10
Herstellung von [Anthrachinon-l.'t-bis-iaminopropyl-y-lN-benzylpiperidiniunDJl-dichloridExample 10
Production of [Anthraquinone-l.'t-bis-iaminopropyl-y-IN-benzylpiperidiniunDJl-dichlorid
CH2-CH2 CH 2 -CH 2
NH - CH2 - CH, - CH2 — NNH - CH 2 - CH, - CH 2 - N
Oi ' |\Oi '| \
2 \ 2 \
CH,CH,
I CH2-CH2 CH2-QH5 CH2-CH2 I CH 2 -CH 2 CH 2 -QH 5 CH 2 -CH 2
NH - CH2 - CH2 -- CH2 - NNH - CH 2 - CH 2 - CH 2 - N
CH,CH,
! CH2-CH2 CH, QH5 ! CH 2 -CH 2 CH, QH 5
Man erhält dieses Produkt, wenn die entsprechende Base in üblicher Weise unter Verwendung von Toluol als Lösungsmittel mit Benzylchlorid unter Rückflußkühlung zur Reaktion gebracht wird. Das erhaltene Produkt schmilzt unter Zersetzung bei 165 bis 1700C.This product is obtained when the corresponding base is reacted with benzyl chloride under reflux in the customary manner using toluene as the solvent. The product obtained melts with decomposition at 165 to 170 ° C.
Beispiele für die Verwendung von erfindungsgemäßen VerbindungenExamples of the use of compounds according to the invention
B e i s ρ i e 1 I Man bereitet folgende Mischung:B e i s ρ i e 1 I Prepare the following mixture:
l,4-Bis-(,<-morpholinoäthyl-amino)-anthrachinon 4,6 g1,4-bis (, <- morpholinoethyl-amino) -anthraquinone 4.6 g
Essigsäure bis zur Erreichung eines pH-Wertes von 4,8Acetic acid until a pH value of 4.8 is reached
Mit Wasser auffüllen auf 100 cm3 Make up to 100 cm 3 with water
Man trägt diese Lösung auf zu 95% weiße Haare auf und läßt 10 bis 15 Minuten bei gewöhnlicher Temperatur einwirken. Nach sehr reichlichem Spülen mit Wasser und Trocknen erhält man eine blaugrüne Färbung der HaareThis solution is applied to 95% white hair and left for 10 to 15 minutes as usual Temperature. After very copious rinsing with water and drying, a blue-green color is obtained Coloring of hair
Beispiel II Man bereitet folgende Mischung:Example II Prepare the following mixture:
IgIg
[Anthrachinon-1,4-bis-(amino-äthyl-/i-[Anthraquinone-1,4-bis- (amino-ethyl- / i-
{N-methyl-morpholininm)}]-bis-{N-methyl-morpholininm)}] - to-
methosulfat methosulfate
mit 10 Mol Äthylenoxyd oxäthylierterwith 10 moles of ethylene oxide oxyethylated
Fettalkohol mit C12-Cw aus Kopra 10 g Na2CO3 bis zur Erreichung einesFatty alcohol with C 12 -C w from copra 10 g Na 2 CO 3 until one is reached
pH-Wertes von 7pH value of 7
Mit Wasser auffüllen auf 100 cm3 Make up to 100 cm 3 with water
Wird diese Lösung unter den selben Bedingungen wie im vorhergehenden Beispiel auf graue Haare aufgetragen, so erhalten sie eine intensive blaue Tönung.Use this solution under the same conditions as in the previous example on gray hair applied, they get an intense blue tint.
Man bereitet folgende Mischung:Prepare the following mixture:
[Anthrachinon-1,8-bis-{ atnino-äth yl-/J-(N-methyl-morpholinium)}]-bis- [Anthraquinone-1,8-bis- {atnino-ethyl- / J- (N-methyl-morpholinium)}] - bis-
methosulfat 0,5 gmethosulfate 0.5 g
Mit 10 bis 11 Mol ÄthylenoxydWith 10 to 11 moles of ethylene oxide
oxäthyliertes Octylphenol 2,5 goxethylated octylphenol 2.5 g
Na2CO3 bis zur Erreichung einesNa 2 CO 3 until one is reached
pH-Wertes von 9,5pH value of 9.5
Mit Wasser auffüllen auf 100 cm3 Make up to 100 cm 3 with water
Wird diese Lösung auf graue Haare während 10 bis Minuten bei gewöhnlicher Temperatur einwirken gelassen, so erhält man nach dem Spülen eine rotviolette Färbung. This solution will apply to gray hair during 10 to Allowed to act for minutes at normal temperature, a red-violet color is obtained after rinsing.
Beispiel IV Man bereitet folgende Mischung:Example IV Prepare the following mixture:
[Anthrachinon-l^-bis-{aminoäthyl-/*- (N-methyi-niorphoHniuin)}]-bfömetbosuUat 4S[Anthraquinone-l ^ -bis- {aminoethyl - / * - (N-methyi-niorphoHniuin)}] - bfömetbosuUat 4 S
NaJ1CO3 bis zur Erreichung eines pH-Wertes von 9NaJ 1 CO 3 until a pH value of 9 is reached
Mit Wasser auffüllen auf 100 cm3 Make up to 100 cm 3 with water
Unter den gleichen Anwendungsbedingungen erhält man eine ähnliche Tönung wie im Beispiel III.A shade similar to that in Example III is obtained under the same conditions of use.
Beispiel V Man bereitet folgende Mischung:Example V Prepare the following mixture:
l,5-Bis-'(/i-morpholinoäthylamino)-anthrachinon 4 g1,5-bis- '(/ i-morpholinoethylamino) -anthraquinone 4 g
Milchsäure bis zur Erreichung eines pH-Wertes Von 4,8Lactic acid until a pH value of 4.8 is reached
Mit Wasser auffüllen auf 100 cm3 Make up to 100 cm 3 with water
Unter den gleichen Bedingungen wie in den vorhergehenden Beispielen erhält man eine rosa Tönung.A pink tint is obtained under the same conditions as in the previous examples.
Beispiel VI Man bereitet folgende Mischung:Example VI Prepare the following mixture:
l,4-Bis-{y-piperidinopropylamino)-anthrachinon 3 g1,4-bis (γ-piperidinopropylamino) anthraquinone 3 g
Milchsäure bis zur Erreichung eines pH-Wertes von 4,8Lactic acid until a pH value of 4.8 is reached
Mit Wasser auffüllen auf 100 cm3 Make up to 100 cm 3 with water
Diese Lösung ergibt unter den gleichen Bedingungen wie in den vorhergehenden Beispielen eine blaßblaue Färbung.This solution gives a pale blue one under the same conditions as in the previous examples Coloring.
Beispiel VII Man bereitet folgende Mischung:Example VII The following mixture is prepared:
[Anthrachinon-1,4-bis-i aminopropyl-y-(N-benzyl-piperidinium)}]-dichlorid . 4,5 g[Anthraquinone-1,4-bis-i aminopropyl-γ- (N-benzyl-piperidinium)}] dichloride . 4.5 g
Natriumbicarbonat bis zur Erreichung eines pH-Wertes von 9Sodium bicarbonate until a pH value of 9 is reached
Mit Wasser auffüllen auf 100 cm3 Make up to 100 cm 3 with water
Bei Anwendung dieser Lösung in der in den vorhergehenden Beispielen beschriebenen Weise während 15 Minuten erhält man eine azurblaue Färbung.When using this solution in the previous one In the manner described in the examples for 15 minutes, an azure blue coloration is obtained.
Beispiel VIIIExample VIII
Man bereitet folgende Mischung:Prepare the following mixture:
4-Nitro-l,3-diaminobenzol 0,1 g4-nitro-1,3-diaminobenzene 0.1 g
[Anthrachinon-hS-bis-jaminoäthyl-/*- (N-methyl-morpholinium)}]-bis-[Anthraquinone-hS-bis-jaminoethyl - / * - (N-methyl-morpholinium)}] - to-
methosulfat Igmethosulfate Ig
[Anthrachinon-l^bis-Jaminoäthyl-/*- (N-methyl-morpholinium)|]-bis-[Anthraquinone-l ^ bis-jaminoethyl - / * - (N-methyl-morpholinium) |] -bis-
methosulfat 1.5 gmethosulfate 1.5 g
[ Anthrachinon-1,5-bis-{aminoäthyl-^- (N-methyl-morpholiniuHiHj-bis-[Anthraquinone-1,5-bis- {aminoethyl - ^ - (N-methyl-morpholiniuHiHj-bis-
methosulfat Igmethosulfate Ig
NH3 bis zur Erreichung einesNH 3 until a
pH-Wertes von 8pH value of 8
Mit Wasser auffüllen auf 100 cm3 Make up to 100 cm 3 with water
Bei Einwirkung dieser Lösung während 10 MinutenWhen exposed to this solution for 10 minutes
te auf 100% weiße Haate bei gewöhnlicher Temperatui erhält man nach dem Spülen. Waschen und Trocknen eine schöne kastanienbraune Färbung mit leicht rosa Reflexen.te on 100% white hair at normal temperature is obtained after rinsing. Washing and drying a beautiful maroon color with light pink reflections.
Claims (1)
Anthrachinonfarbstoffe der allgemeinen FormelClaim:
Anthraquinone dyes of the general formula
CH,-CH,and their quaternization products, in which Z is a radical of the formula
CH, -CH,
CH,-CH,or a residue of the formula
CH, -CH,
Applications Claiming Priority (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR913810A FR1422016A (en) | 1962-10-29 | 1962-10-29 | New anthraquinone dyes and their application to hair dye |
FR920795A FR1391675A (en) | 1963-01-08 | 1963-01-08 | New solutions for hair dyeing and new compounds that can be used in these solutions |
FR930212A FR1401163A (en) | 1963-04-02 | 1963-04-02 | New dyes derived from 2-aminoanthraquinone and their application to hair dyeing |
FR938822A FR1379649A (en) | 1963-06-20 | 1963-06-20 | New anthraquinone dyes and their use for hair dyeing |
US31963563A | 1963-10-24 | 1963-10-24 | |
FR954132A FR87902E (en) | 1962-10-29 | 1963-11-18 | New anthraquinone dyes and their application to hair dye |
US67706867A | 1967-10-23 | 1967-10-23 |
Publications (3)
Publication Number | Publication Date |
---|---|
DE1794385A1 DE1794385A1 (en) | 1974-05-02 |
DE1794385B2 DE1794385B2 (en) | 1974-12-12 |
DE1794385C3 true DE1794385C3 (en) | 1975-07-24 |
Family
ID=27562385
Family Applications (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE1794384*CA Expired DE1794384C3 (en) | 1962-10-29 | 1963-10-29 | Anthraquinone dyes |
DE1492065A Expired DE1492065C3 (en) | 1962-10-29 | 1963-10-29 | Hair dye |
DE1794385*CA Expired DE1794385C3 (en) | 1962-10-29 | 1963-10-29 | Anthraquinone dyes |
DE1794332A Expired DE1794332C3 (en) | 1962-10-29 | 1964-01-04 | Anthraquinone dyes |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE1794384*CA Expired DE1794384C3 (en) | 1962-10-29 | 1963-10-29 | Anthraquinone dyes |
DE1492065A Expired DE1492065C3 (en) | 1962-10-29 | 1963-10-29 | Hair dye |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE1794332A Expired DE1794332C3 (en) | 1962-10-29 | 1964-01-04 | Anthraquinone dyes |
Country Status (6)
Country | Link |
---|---|
US (1) | US3467483A (en) |
BE (1) | BE639298A (en) |
CH (1) | CH434573A (en) |
DE (4) | DE1794384C3 (en) |
GB (1) | GB1053300A (en) |
NL (4) | NL7000658A (en) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1195921B (en) * | 1961-08-12 | 1965-07-01 | Senkingwerk K G | Safety and heating device on heaters fired with bowl burners, in particular room heaters |
US4131676A (en) * | 1977-02-25 | 1978-12-26 | American Cyanamid Company | 2,6-Bis(1-morpholinoalkylideneamino)anthraquinones as anti-amebic agents |
US4138415A (en) * | 1978-05-05 | 1979-02-06 | American Cyanamid Company | 1,4-Bis(aminoalkylamino)-anthraquinones and leuco derivatives thereof |
US4275009A (en) * | 1979-05-29 | 1981-06-23 | American Cyanamid Company | 1-(Aminoalkylamino)-5,8-dihydroxy-4-substituted-anthraquinones |
US4782092A (en) * | 1984-03-02 | 1988-11-01 | Mid-America Cancer Center | 5,8-dichloro-4-hydroxy-1-[(aminoalkyl) amino]-9,10-anthracenediones, pharmaceutical compositions and use |
US5436243A (en) * | 1993-11-17 | 1995-07-25 | Research Triangle Institute Duke University | Aminoanthraquinone derivatives to combat multidrug resistance |
DE4426099A1 (en) * | 1994-07-22 | 1996-01-25 | August Braun | Angular strip with plaster reinforcing material |
FR2766177B1 (en) | 1997-07-16 | 2000-04-14 | Oreal | NOVEL CATIONIC OXIDATION BASES, THEIR USE FOR OXIDATION DYEING OF KERATINIC FIBERS, TINCTORIAL COMPOSITIONS AND DYEING METHODS |
FR2766179B1 (en) | 1997-07-16 | 2000-03-17 | Oreal | NOVEL CATIONIC OXIDATION BASES, THEIR USE FOR OXIDATION DYEING OF KERATINIC FIBERS, TINCTORIAL COMPOSITIONS AND DYEING METHODS |
FR2766178B1 (en) | 1997-07-16 | 2000-03-17 | Oreal | NOVEL CATIONIC OXIDATION BASES, THEIR USE FOR OXIDATION DYEING OF KERATINIC FIBERS, TINCTORIAL COMPOSITIONS AND DYEING METHODS |
FR2786484B1 (en) | 1998-11-30 | 2001-01-05 | Oreal | CATIONIC AMINOANTHRAQUINONES, THEIR USE FOR DYEING KERATINIC FIBERS, TINCTORIAL COMPOSITIONS CONTAINING THEM AND DYEING METHODS |
FR2889954B1 (en) * | 2005-08-26 | 2007-10-19 | Oreal | CATIONIC MIXED DYES COMPRISING ANTHRAQUINONE CHROMOPHORE AND THEIR USE IN CAPILLARY COLOR |
JP5441464B2 (en) * | 2009-03-23 | 2014-03-12 | 富士フイルム株式会社 | Pigment dispersion, ink composition using the same, curable composition, and curable ink composition |
JP5441463B2 (en) * | 2009-03-23 | 2014-03-12 | 富士フイルム株式会社 | Pigment dispersion, ink composition using the same, curable composition, and curable ink composition |
GB201005939D0 (en) * | 2010-04-09 | 2010-05-26 | Biostatus Ltd | Method of analysing a cell or other biological material containing nucleic acid |
DE102012203981A1 (en) | 2012-03-14 | 2013-09-19 | Henkel Ag & Co. Kgaa | Agent for dyeing and / or delustering keratin-containing fibers containing novel 1,4-diaminoanthraquinone dyes |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1856802A (en) * | 1927-02-12 | 1932-05-03 | Soc Of Chemical Ind | Dyestuffs of the anthraquinone series and process of making same |
GB481942A (en) * | 1936-09-17 | 1938-03-17 | Scottish Dyes Ltd | New anthraquinone dyestuffs |
US2311065A (en) * | 1940-02-28 | 1943-02-16 | Eastman Kodak Co | Amino anthraquinones |
DE1078081B (en) * | 1958-02-25 | 1960-03-24 | Thera Chemie Chemisch Therapeu | Preparations for coloring hair or fur |
US3232934A (en) * | 1959-06-25 | 1966-02-01 | Allied Chem | Omega-(1-amino-5 and 8-anthraquinonylamino)-1-ammonium alkanes of 2 to 3 carbon atoms |
BE592616A (en) * | 1959-07-06 | |||
US3123605A (en) * | 1960-01-08 | 1964-03-03 | Basic anthraquinone dyestuffs | |
US3153059A (en) * | 1961-12-20 | 1964-10-13 | Eastman Kodak Co | 1, 4-dihydroxy-2-alkylaminoalkylamino-anthraquinone dye compounds and acrylic materials dyed therewith |
-
0
- GB GB1053300D patent/GB1053300A/en active Active
- NL NL131931D patent/NL131931C/xx active
- BE BE639298D patent/BE639298A/xx unknown
- NL NL299891D patent/NL299891A/xx unknown
-
1963
- 1963-10-29 CH CH1326063A patent/CH434573A/en unknown
- 1963-10-29 DE DE1794384*CA patent/DE1794384C3/en not_active Expired
- 1963-10-29 DE DE1492065A patent/DE1492065C3/en not_active Expired
- 1963-10-29 DE DE1794385*CA patent/DE1794385C3/en not_active Expired
-
1964
- 1964-01-04 DE DE1794332A patent/DE1794332C3/en not_active Expired
-
1967
- 1967-05-19 US US639915A patent/US3467483A/en not_active Expired - Lifetime
-
1970
- 1970-01-16 NL NL7000658A patent/NL7000658A/xx unknown
- 1970-01-16 NL NL7000660A patent/NL7000660A/xx unknown
Also Published As
Publication number | Publication date |
---|---|
DE1794385A1 (en) | 1974-05-02 |
DE1492065C3 (en) | 1975-04-10 |
DE1794384A1 (en) | 1974-05-02 |
US3467483A (en) | 1969-09-16 |
NL131931C (en) | |
CH434573A (en) | 1967-04-30 |
DE1794384B2 (en) | 1974-12-12 |
DE1794384C3 (en) | 1975-07-24 |
DE1794332B2 (en) | 1974-02-28 |
NL7000660A (en) | 1970-04-22 |
DE1492065A1 (en) | 1969-12-18 |
NL7000658A (en) | 1970-04-22 |
DE1794332A1 (en) | 1972-02-10 |
DE1794385B2 (en) | 1974-12-12 |
BE639298A (en) | |
GB1053300A (en) | |
DE1492065B2 (en) | 1973-04-19 |
DE1794332C3 (en) | 1975-01-30 |
NL299891A (en) |
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